CN-121991365-A - Metal organic framework material and preparation method and application thereof

Abstract

The invention provides a metal organic framework material, a preparation method and application thereof, wherein the metal organic framework material comprises a two-dimensional layer formed by coordination of a metal element and a first organic ligand, a column structure formed by coordination of a metal element and a second organic ligand, the two-dimensional layer is connected with the column structure to form a three-dimensional layer-column framework structure, the three-dimensional layer-column framework structure is inserted into each other in a double way to form a first pore canal and a second pore canal, and the area of the first pore canal is The area of the second pore canal is The metal organic framework material provided by the invention has two pore channels with different areas, and can simultaneously realize higher adsorption capacity and selectivity for carbon dioxide when being used for adsorbing the carbon dioxide in the mixed gas containing the carbon dioxide and the nitrogen, thereby realizing high-efficiency capture of the carbon dioxide.

Inventors

• LI YANXI
• LI SHUAI
• GONG QIHAN
• BAI YUHUA
• BO YAWEN
• DING JIAYU
• CHI KEBIN
• SHI DEJUN
• WANG HAO
• ZHANG ZHANQUAN

Assignees

• 中国石油天然气股份有限公司

Dates

Publication Date

20260508

Application Date

20241108

Claims (13)

1. 1. The metal organic framework material is characterized by comprising a two-dimensional layer formed by coordination of a metal element and a first organic ligand, and a column structure formed by coordination of a metal element and a second organic ligand, wherein the two-dimensional layer is connected with the column structure to form a three-dimensional layer-column framework structure, and the three-dimensional layer-column framework structure is inserted into the first pore channel and the second pore channel in a double manner; The area of the first pore canal is The area of the second pore canal is
2. 2. The metal-organic framework material of claim 1 wherein the first cells and the second cells are staggered in a first direction, the length of the first cells in the first direction being less than the length of the second cells in the first direction.
3. 3. The metal-organic framework material of claim 2 wherein the length of the first cell in the first direction is The length of the second pore canal in the first direction is
4. 4. A metal-organic framework material according to any of claims 1-3, characterized in that the first organic ligand comprises a carboxylic acid ligand and the second organic ligand comprises an amide ligand.
5. 5. The metal-organic framework material of claim 1, wherein the three-dimensional layer-column framework structure comprises a first material column distributed along a first direction and a second material column distributed along a second direction, the first material column comprising the first organic ligand and the second material column comprising the second organic ligand, the first and second cells of the metal-organic framework material being defined by the first and second material columns, and wherein a junction of the first and second material columns comprises the metal element.
6. 6. The metal-organic framework material of claim 4 wherein the carboxylic acid-based ligand comprises a compound of formula 1: Wherein R 1 、R 2 is each independently selected from hydrogen, substituted or unsubstituted C1-C8 linear or branched alkyl, substituted or unsubstituted C1-C8 linear or branched alkoxy, amino, hydroxyl, mercapto, halogen, cyano, and derivatives thereof.
7. 7. The metal-organic framework material of claim 4 wherein the amide-based ligand comprises N, N' - (1, 4-phenylene) diisonicotinamide.
8. 8. The metal-organic framework material of claim 1 wherein the metallic element comprises at least one of copper, zinc, magnesium, iron, manganese, cobalt, and nickel.
9. 9. A method for producing a metal-organic framework material according to any one of claims 1 to 8, characterized by comprising the step of subjecting a raw material system comprising an amide ligand, a carboxylic acid ligand and a metal element to a solvothermal reaction to obtain the metal-organic framework material.
10. 10. The method of claim 9, wherein the solvothermal reaction is at a temperature of 50 ℃ to 200 ℃; And/or the solvothermal reaction time is 4-96 hours; and/or the molar ratio of the metal element to the carboxylic acid ligand is 1 (0.1-5); and/or the molar ratio of the metal element to the amide ligand is 1 (0.1-5).
11. 11. Use of a metal organic framework material according to any one of claims 1-8 in an adsorption column.
12. 12. Use of a metal organic framework material according to any one of claims 1-8 in a fixed bed.
13. 13. Use of a metal organic framework material according to any one of claims 1-8 in carbon dioxide/nitrogen adsorptive separation.

Description

Metal organic framework material and preparation method and application thereof Technical Field The invention belongs to the technical field of adsorption separation, and particularly relates to a metal organic framework material and a preparation method and application thereof. Background With the development of technology and the improvement of human living standard, the demand of human beings for fossil energy is growing, thereby bringing about serious energy crisis and environmental pollution. One of the main manifestations of environmental pollution is the greenhouse effect, which is unprecedented. The carbon dioxide released in the air is mainly from the exhaust gas of the fuel engine, and the main components of the carbon dioxide are 75% of nitrogen, 10-15% of carbon dioxide, 7% of water vapor and a small amount of oxidative corrosive gas. Therefore, the efficient realization of carbon dioxide and nitrogen selective adsorption separation is a main criterion of carbon dioxide adsorbents. Literature Exquisitely Constructing a Robust MOF with Dual Pore Sizes for Efficient CO 2 Capture discloses the use of dual pore metal organic framework materials for adsorbing carbon dioxide from a mixed gas containing carbon dioxide and nitrogen, with pore sizes of respectivelyAndThe pore canal has smaller size, and correspondingly, the adsorption capacity and the adsorption selectivity to carbon dioxide are lower. Literature Tuning CO2 Selective Adsorption over N2 and CH4 in UiO-67Analogues through Ligand Functionalizatio discloses the preparation of a metal organic framework material BUT-10, which has a CO 2 adsorption capacity up to 100mg/g, BUT a selectivity of only 18, and its use in carbon dioxide/nitrogen separation. Literature Optimized Pore Nanospace through the Construction of a Cagelike Metal-Organic Framework for CO2/N2 Separation discloses the preparation of a metal organic framework material FJUT-4 and its use in carbon dioxide/nitrogen separations, the material having a CO 2 selectivity of 69, but only an adsorption capacity of 44mg/g. In summary, when the existing adsorption materials adsorb carbon dioxide in a mixed gas of carbon dioxide and nitrogen, it is often difficult to achieve both high adsorption capacity and high selectivity, which limits their practical application. Disclosure of Invention The main object of the present invention is to provide a metal organic framework material which can realize a high adsorption capacity and a high selectivity for carbon dioxide when used for adsorbing carbon dioxide in a mixed gas containing carbon dioxide and nitrogen. The invention also provides a preparation method of the metal organic frame material, which can prepare the metal organic frame material, and has simple process and low cost. The invention also provides an adsorption column, which comprises the metal organic framework material, so that the adsorption column can realize higher adsorption capacity and higher selectivity for carbon dioxide when being used for carrying out adsorption separation on the mixed gas containing carbon dioxide and nitrogen. The invention also provides a fixed bed, which comprises the metal organic framework material or the adsorption column, so that the fixed bed can realize higher adsorption capacity and higher selectivity for carbon dioxide when used for carrying out adsorption separation on the mixed gas containing carbon dioxide and nitrogen. The invention also provides a method for absorbing and separating carbon dioxide/nitrogen, which uses the metal organic frame material or the absorption column or the fixed bed to absorb the mixed gas containing carbon dioxide and nitrogen, so that the absorption and separation method can realize higher absorption capacity and higher selectivity for carbon dioxide. In a first aspect, the present invention provides a metal-organic framework material, where the metal-organic framework material includes a two-dimensional layer formed by coordination of a metal element and a first organic ligand, and a column structure formed by coordination of a metal element and a second organic ligand, where the two-dimensional layer is connected with the column structure to form a three-dimensional layer-column framework structure, and the three-dimensional layer-column framework structure is inserted into the two-dimensional layer-column framework structure to form a first pore channel and a second pore channel; The area of the first pore canal is The area of the second pore canal is In the metal organic framework material, the first pore channels and the second pore channels are staggered in a first direction, and the length of the first pore channels in the first direction is smaller than that of the second pore channels in the first direction. The metal organic frame material as described above, wherein the length of the first pore canal in the first direction isThe length of the second pore canal in the first direction is The metal orga